Aliphatic polyepoxide treated derivatives of alkylene oxide-amine modified-phenolic resins, and method of making same



ALHPHATEC POLYEPQXIDE TREATED DERIVA- TiVlES OF ALKYLENE flXlDE-AMTNE MODE- FiED-PHENOLHC RESINS, AND METHOD OF WEARING SAME Melvin De Groote, St. Louis, and KWan-Ting Sheri, Erent wood, Mm, assignors to Petrolite Corporation, Wilmtngton, DeL, .a corporation of Delaware No Drawing. Original application .lune 10, 1953, Serial No. 360,843, now Patent No. 2,792,362, dated May 14,

1957. Divided and this application September 11, 1956, Serial No. 609,093

7 Claims. at. 260-45) or procedures particularly adapted for preventing, breaking or resolving emulsions of the w'ater-in'cil type and particularly petroleum emulsions. Our invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

The present invention is concerned with a 3-step manu-. facturing processinvolving (1) condensing certain phenol aldehyde resins, hereinafter described in detail, with certain basic non-hydroxylated polyamines, hereinafter described in detail, and formaldehyde; (2) oxyalkylation of the condensation product with certain monoepoxides, hereinafter described in detail; and (3) oxyalkylation of the previously oxyalkylated resin condensate with certain non-aryl polyepoxides, also hereinafter described in detail.

The present invention is characterized by the use of compounds derived from diglycidyl ethers which do not introduce any hydrophobe properties in its usual meaning but in fact are more apt to introduce hydrophile properties. Thus, the diepoxides employed in the present invention are characterized by the fact that the divalent radical connecting the terminal epoxide radicals contains less than 5 carbon atoms in an uninterrupted chain.

The diepoxides employed in the present process are obtained from glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triprcpylene glycol, glycerol, diglycerol, triglycerol, and similar compounds. Such products are Well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be nonaryl or aliphatic in character. The diglycidyl ethers of co-pending application, Serial No. 350,533, are invariably andinevitably aryl in character.

The diepoxides employed in the present process are usually obtained by reacting a glycol or equivalent compound, such as glycerol or diglycerol, with epichlorohydrin and subsequently with an alkali. Such diepoxides have been described in the literature and particularly the patent literature.

Reference to being thermoplastic characterizes products as being liquids at'ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to-diiferentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it sometimes is desirable to dilute the compound containing the epoxy rings before reacting with an oxyalkylated aminev condensate. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as, for example, kerosene, benzene, toluene, dioxane, possibly various ketones, chlorinated solvents, dibutyl ether, dihexyl-ether, ethylene glycol diethylether, 'diethyl'eneglycol diethylether', and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes re ferred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the Word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-epoxide rings or oxirane rings in the alpha omega position. This is a departure from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane (1,2-3,4- diepoxybutane).

It well may be that even though the previously suggested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher.

molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric compounds containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins. Simply for purpose of illustration to show a typical diglycidyl ether of the kind herein employed reference is made to the following formula:

or if derived from cyclic diglycerol the structure would be thus:

or the equivalent compound wherein the ring structure involves only6 atoms, thus:

I n ire-04 211 no o-cn Ben O Commercially available compoundsseem to be largely the former with comparatively small amounts, intact, comparatively minor amounts,.,of the latter.

Having obtained an acyclic reactant having generally 2 epoxy rings as depicted in thenext to last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place'withany oxyalkylated phenolaldehyde resin condensate ,by virture. of the fact.

that there are always present either phenolic hydroxyl radicalsor alkanol radicalsresulting from the oxyalkylation of thephenolic hydroxyl radicals; therernay be present reactive hydrogen atoms attached to a nitrogen atom or any oxygen atom, depending on whether initially there was, present a hydroxylated group attached to an amino hydrogen, group or a secondary amino group. .In any event there is always a multiplicity of reactive hydrogen atoms present in the oxyalkylated amine-modified phenol-aldehyde resin.

To illustrate the products which represent the subject matter of thepresent invention referenceiwill be made to a reactioninvolving a mole ofthe oxyalkylating agent, i. e., the compound having 2 oxirane rings and an oxyalkylated amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of 2 moles of the oxyalkylated amine condensate to one mole of the oxyalkylating agent gives a product which-may be indicated as follows:

in which n is a small whole number less than l0,.and usually less than 4, and-including O, and R 'represents a divalent radical as previously described being free from any radical having more than 4. uninterrupted carbon atoms in a single'chain, and 'tliecharacterization oxyalkylated condensate is simply an abbreviation for the condensate which is described in greater detail subsequently. I

Such final product in turn also must be soluble "but solubility is not limited'to' an'organicgso'lvent but may include water, or for that matter; as'olution'of water containing an acid such as hydrochloric acid,;:acetic acid, hydroxyacetic acid, etc. In other words, the: nitrogen groups present, whether two or "more, may-or rnay not be significantly basic and it is immaterial whether'aqueous solubility represents an-anhydro base or the free/base (combination with Water) or, a salt form such as the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this properly serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize, the factthat in many instances, the

preferred compounds have distinct water s olu bil'i'ty or are.

distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their weight of 5% gluconic acid, at ordinary temperature and ShOWLlat least some 'tendency'towards being self-dispersing. The. solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone. As oxyalkylation proceeds the significance of the basicity of any nitrogen group is obviously diminished.

The polyepoxide-treated condensates obtained in the manner described are, in turn, oxyalkylation-susceptible and valuable derivatives can be obtained by further reaction with ethylene oxide, propylene oxide, ethylene imine, etc.

Similarly, the polyepoxide-derived compounds can be reacted with a product having both a nitrogen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. 5. Patent No. 2,520,093, dated August 22, 1950, to Gross.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid Washing of building stone and brick; 'as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various'trade wastes and the like; as germi' cides, insecticides, emulsifying agents, as, for example for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

As far as the use of the herein described products goes for purpose ofresolution of petroleum emulsions of the Water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufficiently hydrophile character to at least meet the testsetforth in U. 5. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the variouscondensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably'a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience, what is saidhereinafter will be divided into eight parts:

Part 1 is concerned with the hydrophile nonaryl polyepoxides and particularly diepoxides employed as reactants;

Part 2 is concernedwith the phenol-aldehyde resin which is subjected to modification by condensation reactionto yield an amine-modified resin;

Part 3 is concerned with basic nonhydroxylated polyar'nines having at least one secondary amino group and Part is concerned with the oxyalkylation of the products described in Part 4, preceding;

Part 6 is concerned with reactions involving the two preceding types of materials and examples obtained by such reactions. Generally speaking, this involves nothing more than a reaction between two moles of a previously prepared oxyalkylated amine-modified phenol-aldehyde resin condensate as described and one mole of a polyepoxide so as to yield a new and larger resin molecule or comparable product;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 8 is concerned with uses for the products herein described either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART, 1

Reference is made to various patents as illustrated in the manufacture of the nonaryl polyepoxides and particularly diepoxides employed as reactants in the instant invention. More specifically, such patents are the following: Italian Patent No. 400,973, dated August 8, 1941; British Patent No. 518,057, dated December 10, 1938; U. S. Patent No. 2,070,990, dated February 16, 1937 to Groll et al.; and U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech. The simplest diepoxide is probably the one derived from 1,3-butadiene or isoprene. Such derivatives are obtained by the use of peroxides or by other suitable means and the diglycidyl ethers may be indicated thus:

In some instances the compounds are essentially derivatives of etherized epichlorohydrin or methyl epichlorohydrin. Needless to say, such compounds can be derived from glycerol monochlo-rohydrin by etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent No. 400,973:

Another type of diepoxide is diisobutenyl dioxide as described in aforementioned U. S. Patent No. 2,070,990, dated February 16, 1937, to Groll, and is of the following formula H2C/\\C-CH2-CH2(IJ-/ECH2 CH3 CH3 The diepoxides previously described may be indicated by the following formula:

H R R H HC-\7C[R"] 'C\'/'CH O O in which R represents a hydrogen atom or methyl radical and R" represents the divalent radical uniting the two terminal epoxide groups, and n is the numeral 0 or 1.

As previously pointed out, in the case of the butadiene derivative, n is 0. In the case of diisobutenyl dioxide R" is CH CH and n is l. In another example previously referred to R" is CH OCH and n is 1.

However, for practical purposes the only diepoxide available in quantities other than laboratory quantities is a derivative of glycerol or epichlorohydrin. This particular diepoxide is obtained from diglycerol which is largely acyclic diglycerol, and epichlorohydrin or equivalent thereof in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one-of a number of glycols or polyglycols and it is more convenient to include as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl epichlorohydrin. So presented the formula becomes:

In the above formula R is selected from groups such as the following: i

means that is derived actually or theoretically, or at least derivable, from the diol HOROH, in which the oxygen-linked hydrogen atoms were replaced by Thus, R(OH),,, where n represents a small whole number which is 2 or more, must be water-soluble. Such limitation excludes polyepoxides if actually derived or theoretically derived at least, from water-insoluble diols or water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms or thereabouts.

Referring to a compound of the type above in the formula in which R is C H (OH) it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, if R happened to be C H (OH)OC H (OH), one could obtain a tetraepoxide. Actually, such procedure generally 7 yields triepoxides, or-rnixtures with'higher epoxides. and perhaps in other instances mixtures in which diep'oxides are also present. Our preference is to use the diepoxides. There is available-commerciallyat least one diglycidyl ether free from aryl. groups and also free from any radical having or more carbon atoms inyanuninterrupted chain.

This .particular .diglycidyl ether. is obtained by the: use of epichlorohydrin in -.such a manner that approximately 4 moles of, epichlorohydrin yield one mole of the diglycidyl ether, or, stated another 'way, -it can be consideredas being formed from'one r'noleof; diglyeerol and 2 moles of epichlorohydrinso as to-give the appropriate diepoxide. The molecular weight is approximately 370' and the number of epoxidegroups a per. molecule are approximately 2. For this reason in the-firsti of a series of subsequent examples this particular diglycidyl ether is used, although obviously any of the others previously described would be just as suitable. Forconvenience, this diepoxide will be referred to as diglycidyl ether A. Such material corresponds in a general way tothepreviousformula.

Using laboratory-procedure we have reacted diethyleneglycol with epichlorohydrin and subsequently with alkali was to produce a product which, on examination, "corresponded approximately to the following compound:

The molecular weight of the'product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, is in. grams instead of pounds.

Probably the simplest terminology for these polyepoxides, and particularly *diepoxides, to differentiate from comparable aryl compounds is to..1use.-the t'erminology epoxyalkanes and, more particularly,. polyepoxyalkanes or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in :which a carbon atom chain is interrupted by an oxygenatom, and, thus, they not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a heterocyclic ring. The principal. class properly may bereferred to as polyepoxypolyg1yceols,. or diepdxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetone so as to form the 5-membered ring, followed by conversion of the terminal hydroxyl groups into epoxy radicals.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably l0or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei variesfrom 3 to, 6, i. e., n varies from 1 to 4; R repre- 8 sents an aliphatic hydrocarbon substituent, generally an alkyl radical. having from 4 to 15 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde :it may, of course, be derived from any other reactive'aldehyde having 8 carbon atoms 'or less.

Because -a resin is 1 organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This' is..particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance, paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol die'thylether. Sometimes a mixture of the two solvents (oxygenated andnOn-oXygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in 'a non'ox-yge'nated solvent, such as benzene or xylene. This presents no problem insofar that all that is*required is to make a solubility test on commercial :available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible,

Y fusible, "nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resins having an average molecular weight corresponding to at least 3 andnot over 6 phenolic nuclei per resin molecule. These resins are'difun'ction'al only in regard to methylol-formingreactivity, are 'derivedfby reaction between a difunctional monohy'driclphenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol, and are formed in the substantial absence of trifunctional. phenols. The phenol is of the formula The basic nonhydroxylated amine may be designed thus:

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance,:2.1noles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

in which R" is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

Table I M01. Wt.

Ex- R of resin ample R Position derived 7L molecule number of R from- (based on n+2) Tertiary butyl Para-.. Formal- 3.5 882.5

Secondary butyl 3. 5 882. 5 Tertiary amyl... 3.5 959.5 Mixed secondary 3.5 805.5

and tertiary amyl. Propyl 3.5 805.5 Tertiary hexy 3. 5 1, 036. 5 oty 3. 5 1, 190. 5 NonyL- 3. 5 1, 267. 5 DecyL. 3. 5 1, 344. 5 Dodeey 3. 5 1, 498. 5 Tertiary butyl 3. 5 945. 5

Tertiary amyl 3. 5 1, 022. 5 1 3.5 1,330.5 Tertiary butyl 3. 5 1, 071. 5

Tertiary amyl. 3. 5 l, 148. 5 16a onyl d0 3.5 1,456.5 17a Tertiary butyl Propi 3.5 1, 008.5

dehyde.

18a Tertiary amyl do 3.5 1,085.5 19a Nony 3.5 1,393.5 2011 Tertiary butyl 4.2 996.6

2112 Tertiary amyl 4.2 1,083.4 22a ony 4.2 1, 430.6 23a Tertiary butyL- 4.8 1,094.4 2412 Tertiary amyL 4.8 1,189.6 4.8 1, 570.4 1.5 604.0 1.5 653.0 1.5 688.0

PART 3 As has been pointed out, the amine herein employed as a reactant is a basic secondary polyamine and preferably a strongly basic secondary polyamine free from hydroxyl groups, free from primary amino groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl alicyclic, arylalkyl, or heterocyclic in character.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amino group. By way of example the following formulas are included. It will be noted they include some polyamines which, instead of being obtained from ethylene dichloride, propylene dichloride, or the like, are obtained from dichloroethyl ethers in which the divalent radical has a carbon atom chain interrupted by an oxygen atom:

CH; CH: j H V H N propyleneNpropyleneN H H Another procedure for producing suitable polyamines is a'reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed" by an alkylating agent of the kind described, for example, dimetltylsulfate, or else a reaction which involves an alkylene oxide, such as ethylene oxide or propylene oxide, followed by the use of an alkylating agent or the comparable procedure in which a halide is used.

What has been said previously may be illustrated by reactions involving asecondary-alkyl amine, ora secondary aralkyl amine, or-a secondary alicyclic amine, such as dibutylarnine, dibenzylamine, dicyclohcxylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylating agent, such as dimethyl sulfate. In a somewhat similar procedure the secondary amine of the kind just specified can be reacted with an alkylene oxide such as ethylene oxide, propylene oxide, or the like, and then reacted with an imine followed by the final step noted above in order to convert the primary amino group into a secondary amino group.

Reactions involving the same two classes of reactants previously described, i. e., a secondary amine plus an imine plus an alkylating agent, or a secondary amine plus an alkylene oxide plus an imine plus an alkylating agent, can be applied to another class of primary amines which are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula in which x is a small whole number having a value of l or more, and may be as muchas 10101 12; n is an integer having a value of 2 to4, inclusive; m represents simplification.

to Spence. The latter patent describes typical haloalkyl tethers such as CH OC H CI -CH2-CH2 CH1 CHOHzOCzH4OC2N4Br Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups'attached to nitrogen is typified by R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents men tioned immediately preceding. Monoamines so obtained and suitable for conversion into appropriate polyamines are exemplified by Other somewhat similar secondary monoamines equally suitable for such conversion reactions in order --to yield appropriate secondary amines, are'those of the composition RO(CH2) R*O(GH;4)3

asdescribed in'U. S. Patent No. 2,375,659, dated May 8, 1945, to'lones et al. Inthe above-formulaR maybe methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary amines-which can be converted 'into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the :alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta phenoxyethylamine, gamma phenoxypropylamine, beta-phenoxy alpha-methylethylamine, and beta-phenoxypropylamine.

Othersecondary 'monoamines suitable for conversion into polyamines are the kind described in British Patent No, 456,517 and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as with the statement that such presentation is an over- It was pointed out that at least one ocmetres NpropyleneNpropyleneN In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as differentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two different structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a. large variety of compounds might be obtained due to such multiplicity of reactive radicals. This can be illustrated by the following formula:

Over and above the specific examples which have appeared previously, attention is directed to the fact that added suitable polyamines are shown in subsequent Table II.

PART 4 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethylene glycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necesary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difficult perhaps to add a solid material instead of the liquid solution, and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicles such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circum- 15 stances. On theother hand, if the products are not mutually soluble then agitation should be'more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such "as "benzene or xylene. Refluxing should be long enough to insure"that the"resin added, preferably in a powdered form, is completely d1ssolved. However, if the resin isprepared as such it may be added in solution'form, just aspreparation is described -in aforementioned U. '8. Patent 2,499,368. After the resinis in complete solution'thejpolyamine is added and stirred. Depending on thepolyamineselected, t may or maynot be soluble in the'resin'solution. If t is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. "If so,'the-r'esin then will dissolve inthe formaldehyde solution as added, and if not, it is even possiblethat the initial'reaction mass could be a three-phase'system instead 'of a twophase system although this would be extremely unusual. This solution, or mechanical mixture, if inotfcomp'letely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower,

provided this initial low temperature stage is employed.

The formaldehyde is then added inasuitable form. For reasons pointed out we prefer to usea solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale'manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not'true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

-Returning again to the preferredmethod'of' reaction and particularly from the'standpo'int of laboratory'procedure employing a glass resin pot, when'the reaction has proceeded as one can reasonably expect ata'low temperature, for instance, after holding theirea'ction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to -24 hours, we then complete the reaction by raising the temperature upto 150 C., or thereabouts as required. The'initial low temperature procedure can be eliminated or reduced tomerelythe shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water 'of 'reactionand the water of solution of the formaldehyde is eliminated. 'We then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C. and below 150 C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range.

This period of heating and refluxing, after the 'water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary 'polyamine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight. excess of formaldehyde and,-again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any..particular advantage in so doing. Whenever feasible we have checked .the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and

' was noted.

several hours.

particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present,

'is another index.

The phenol-aldehyde resin is the one that has been identified previously as Example .1a. 'It was obtained ;from a para-tertiary butylphenol and formaldehyde.

The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weightof tl1e5resin .was 882.5. This corresponded toan average of about 3 /2, phenolic nuclei, vas

the value for n which excludesthe 2 external nuclei, i. e.,

the resinwas largely amixture having 3 nuclei and 4 nuclei, excluding the 2 external-nuclei, or 5 and 6 overall nuclei. Theresin so obtained inaneutralstate had a light amber color.

882 grams'of theresin identified as la preceding were powdered and mixed with a somewhat lesser weight of xylene, i. e., 600 grams. The mixture was refluxed until -solution was complete. .It was then'adjusted to approximately 30 to 35 C., and 176 grams of symmetrical dimethylethylene diamine added. The mixture was stirred vigorously and formaldehyde added slowly. In thisparticulan instance the formaldehyde used was a 30% solution and 200 grams were employed which were addedin a little short of 3 hours. The mixture was .stirredvigorously and kept within a temperature range of 30 to 46 C. for about 19.hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of unreacted formaldehyde Any unreacted formaldehyde seemed to disappear within approximately two to three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 152 C., or slightly higher. .Themass waskept at this higher temperature for three to'four hours and. reaction stopped. During this time, any additional water which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat less than 30 hours. In other examples, it varied from a little over 20 hours up to 36 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of Then refluxing was employed until the odor of formaldehyde disappeared. After the .odor of formaldehyde disappeared the phase-separating trap was employed-to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of to C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

Table II Strength of Reac- Reac- Max. Ex. Resin Amt, Amine used and amount tormalde- Solvent used tion, tion distill. No. used grs. hyde soln. and amt. tern time, temp,

and amt. hrs. 0.

Xylene600g 20-23 26 152 1b 1a 882 Amme A 176 g Xylene 450 g 21-21 24 150 Xylene 550 g. 20-22 28 151 Xylene 400 g-- 20-28 36 144 N Xylene 450 g 22-30 25 156 Xylene 600 g 21-28 32 150 Xylene 600 gm. 21-23 30 145 35 148 Xylene 500 g. 35 143 Xylene 425 g 20-22 31 145 ylene 500 g 21-2g Amin D 11 y ene 550 g 22-2 441 Aming E 155 5. Xylene 400 g 25-38 32 150 480 Amine E 158 g- Xylene 400 g 21-24 30 152 W it? 441 Amin F191 01 gr... yene g 480 e g 30% 100 g. X 22-27 29 143 23-25 36 149 21-26 32 148 21-23 30 148 -26 36 152 Amin H282 37 81g y ene g r Aming H 141 g 30% 50 g-.. Xylene 350 gm... 21-22 28 151 As to the formulas of the above amines referred to as Amine A through Amine H, inclusive, see immediately below:

Example 10 The oxyalkylation-susceptible compound employed is the one previously described and designated as Example 1b. Condensate 1b was in turn obtained from symmetrical dimethylethylene diamine and the resin previously identified as Example 1a and formaldehyde. Reference to Table I shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde. 10.82 pounds of this resin condensate were dissolved in 6 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a'temperature of approximately C. to C., and at a pressure of about 15 to 20 or 25 pounds, 25 pounds at the most. In some subsequent examples pressures up to 35 pounds were employed.

The time regulator was set so as to inject the ethylene oxide in approximately three-quarters of an hour and then continue stirring for 15 minutes or longer, a total time of one hour. The reaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 10.82 pounds. This represented a molal ratio of 24.6 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2164. A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables V and VI.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxylkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a dilferent oxide.

Example 20 This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example 1b, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example 10), to wit, 10.82 pounds. The amount of oxide present in the initial step was 10.82 pounds, and the amount of solvent remained the same. The amount of oxide added was" another 10.82 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step thev '19 amount of oxide added was a total of 21.64 pounds and the molal ratio of ethylene oxide to resin condensate wa:649.2 to l. The theoretical molecular weight was 32 The maximum temperature during the operation was 125 to 130 C. The maximum pressure was in the range of to pounds. The time period was one and three-quarter hours.

Example Theoxyalkylation proceeded in the same manner described in Examples 10 and 20. There was no added solvent and no added catalyst. The oxide added was 10.82 pounds and the total oxide at the end of the oxyethylation step was 32.46 pounds. The molal ratio of oxide to condensate was 73.8 to 1. Conditions as far as temperature and pressure and time were concerned were all the same as in Examples 10 and 2c. The time period was somewhat longer than in previous examples, to wit, 2 hours.

Example The oxyethylation was continued and the amount of oxide added again was 10.82 pounds. There was no added catalyst and no added olvent. The theoretical molecular weight at the end of the reaction period was 5410. The molal ratio of oxide to condensate was 98.4 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 2 /2 hours. The recation unquestionably began to slow up somewhat.

Example 5 c The oxyethylation continued with the introduction of another 10.82 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitation period was 6492, and the molal ratio of oxide to resin condensate was 123 to l. The time period, however, dropped to 2 hours. Operating temperature and pressure remained the same as in the previous example.

Example 60 The same procedure was followed as in the previous examples. The amount of oxide added was another 10.82 pounds, bringing the total oxide introduced to 64.92pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period was 3 hours.

Example 70 The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 75.74 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8656. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 4 hours.

Example 8c This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 86.56 pounds. The theoretical molecular weight was 9738. The molal ratio of oxide to resin condensate was 196.8 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 5 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxy- 20 ethylation was started in a l5-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 10 through 400 were obtained by the use of ethylene oxide, whereas 410 through 800 were obtainedv by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples 10 through 40c, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 15th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 8th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 8 coincides with the figure in column 3.

Column 9 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 10 can be ignored insofar that no piopylene oxide was employed.

Column 11 shows the catalyst at the end of the reaction period.

Column 12 shows the amount of solvent at the end of the reaction period.

Column 13 shows the molal ratio of ethylene oxide to condensate.

Column 14 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 1c, 2c, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV, Examples 410 through 800 are the counterparts of Examples 1c through 400, except that the oxide employed is propylene oxide instead of. ethylene oxide. Therefore, as explained previously, four columns are blank, to wit, columns 4 and 9.

Reference is now made to Table V. It is to be noted these compounds are designated by d numbers, 1d, 2d, 311, etc., through and including 32d. They are derived, in turn, from compounds in the 0 series, for example, 36c, 40c, 54c and 700. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 10 through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from If de- The The reason Propl. based oxide on thecmpd.

Molal ratio oxide alkyl. suscept. suscept.

Ethyl.

cmpd.

Such distillation also Condensation of a nitrog- Composition at and Oxyalkylation generally tends to yield lighter The products resulting from these procedures may Obviously, in the use of ethylene oxide and propylene Needless to say, one could start with ethylene oxide t" l s 00000033300003333000033330000333300003333 fi m IILLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL W 1 1 e Wm I P0 s 7 246802468642086448260 82628 06058123456700 t. O Llawd i mfiLamilomLamilA nmomQlinmkOWKRMZZLQWRM fiwL7 2 7 9m n, 2222222288888888444444446666666622222222 d 8880088888888888800000000555555 058880088800 b 000000 001L111111222222224m444444400000000 0m 1 111111111111111.1111111111111111 1111 c The" data given in regard to the operating conditions The colors of the products usually vary from a reddish is substantially the same as before and appears in Table VI.

contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. sired the solvent may be removed by distillation, and particularly vacuum distillation. may remove traces or small amounts of uncombined 10 oxide, if present and volatile under the conditions employed.

oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indiiferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant.

and then use propylene oxide, and then go back to ethyluse ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

amber tint to a definitely red, and amber. is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. enous product invariably yields a darker product than the original resin and usually has a reddish color. solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent.

Table III Solvent,

lbs.

, and

, the initial 0 series such Then oxyalkylation proa r 1111111111111111111111111111111111111111 C e r :0. L wds H tfl 0 Po t .1 S u I 6802 8642086 482604 628 062 1234567 m. mm w .864219 8765421 m00l122 H516%839 "4826048 t- 12344 1357913 2 68024 493827 5061727 m m Mme 3456 m1234578 -1M34678 m124578w 0 m 112233 0 O u 6 622222322 d 5 588888888 b 44444 4 4 4 0 fim0 0 O 0 0 0 oml 1.111111111111111 0 H n u n p d ...N as b m 1111111 o. W m N n x ccccccc E 4567890 3333334 360 and 400, involve the use of ethylene oxide first propylene oxide afterward.

obtained from 540 and 700 obviously come from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small 5 letter d, as 1d, 2d, 3d as 360, 40c, 54c, and 70c, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. ceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 360, consisted of the reaction product involving 10.82 pounds of the resin condensate, 16.23 pounds of ethylene oxide, 1.0 pound of caustic soda, and 6.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i. e., the catalyst 20 ene oxide; or, inversely, start with propylene oxide, then present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any.

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylation step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of the next step, except obviously at the very start the value depends on the theoretical molecular weight at the end of the initial oxyalkylation step; i. e., oxyethylation for 1d through 16d, and oxypropylation for 17d through 32d.

It will be noted also that under the molal ratio the values of both oxides to the resin condensate are included. 35 colored products and the more oxide employed the lighter Oxyalkylation-susceptible.

Molec. wt. based on theoi'etical value Molec. wt.

oretical value oxide cmpd.

Propl. based oxide ontheto oxycmpd.

Molalratio Ethyl. Propl.

oxide to oxyto oxyalkyl. alkyl. suscept. suscept. cmpd.

0 001 6 30 5011223450 23457850.005556008877653 mum-OM93 0246804822 68048 25702727 1234680 1 2 1112 111 11122 .1

98775332988533213 33. 3 5 IZQUGBDN 1 0 33 5 a 5555 Molal ratio Ethyl. oxide to oxyalkyl. alkyl. suscept. suscept.

cmpd.

Solvent, lbs.

Solvent, lbs.

Composition at end lyst, lbs.

0000000000000000555VJ5FJ5500000,000

Composition at end oxide,

Ethl. Pi'opl. Catnoxide,

O-Sd" 11%.

a l ES 1.1111111111111111111111111111111 W 12347901123590126666666622222222 mum 48268615482061591111111199999999 w b 5 O 6 L7 &4qMiflnmv omdnflwinmow w mnmnmavmLLLLLLLL Xl. 1123455 11245568888888800000000 P0 11111111 4444444488 8 88482606824 604 2 6666666622%2%%22988776556%52oo1m% t LLL LLLLlomqwnmnaoaowiiLlqmqwiL- 7 Lfimfim m 222m2222 4444444 1122344 um223z o Table I V Solvent, lbs.

Table 'V Solvent, lbs.

oxide, lyst,

lbs.

00000555333338884444444455555555 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL Propl. Oata "oxide, lyst,

Composition before Ethl. Propl. Cataoxide, lbs.

Composition before Ethl. oxide,

lbs.

, cmpd,

Ex. N0.

* Oxyalkylatlon-susceptible.

Ex. No.

Oxyalkylation-susoeptlble.

the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more diflicult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The

preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

Table VI Max. Max Solubility Ex. temp pres., Time, No. C. p. s. 1. hrs.

Water Xylene Kerosene 125-130 15-25 2 125-130 15-25 2% 125-130 15-25 2 125-130 15-25 3 125-130 15-25 4 125-130 15-25 125-135 20-25 1 125-135 20-25 1% 125-135 20-25 1% 125-135 20-25 2% 125-135 20-25 2 125-135 20-25 3 125-135 20-25 4 125-135 20-25 5 125-135 -25 2 125-135 15-25 2 125-135 15-25 2% 125-135 15-25 4 125-135 15-25 3 125-135 15-25 3% 125-135 15-25 4 125-135 15-25 5 130-135 15-20 1 130-135 15-20 1% 130-135 15-20 2 130-135 15-20 3 290. 130-135 15-20 2 300. 130-135 15-20 2% 310. 130-135 15-20 3 32a. 130-135 15-20 3 do.. 330. 130-135 -30 Insoluble 34c. 130-135 20-30 do 350. 130-135 20-30 1 Emulslfiable-- 36c. 130-135 20-30 2% do 370. 130-135 20-30 2 380. 130-135 20-30 3 390. 130-135 20-30 4 40c- 130-135 20-30 4 410. 125-130 20-25 1 Insoluble. 42c. 125-130 20-25 1% Do. 430. 125-130 20-25 1% D0. 44c 125-130 20-25 2 Soluble. 45c. 125-130 20-25 3 D0. 460. 125-130 20-25 3 D0. 470. 125-130 20-25 3 D0. 48c- 125-130 20-25 3 D0. 490. 130-135 30-35 2 Insoluble 50c. 130-135 30-35 2% Do. 510. 130-135 30-35 3 Do. 520. 130-135 30-35 4 Soluble. 53c. 130-135 30-35 4% Do. 54c 130-135 30-35 3 Do. 55c..- 130-135 30-35 4 Do. 5fie.. 130-135 30-35 5 Do. 570... -135 15-20 2 Insoluble 58c-.. 125-135 15-20 2% D0. 690... 125-135 15-20 3 Do. 600... 125-135 15-20 4 D0. 61c 125-135 15-20 4 D0. 620... 125-135 15-20 3% Soluble. 63c 125-135 15-20 4 D0. 640... 125-135 15-20 5 D0. 650... -140 5-10 2% Insoluble 66o. 130-140 5-10 2% D0. 670... 130-140 5-10 3 Do. 680... 130-140 5-10 4 Soluble. 69c.-- 130-140 5-10 5 D0. 700. 130-140 5-10 4 Do. 71c. 130-140 5-10 5 D0. 72c 130-140 5-10 0 Do. 730. 125-130 15-20 1% Insoluble 74c- 125-130 15-20 2 Do. 750. 125-130 15-20 2 D0. 76e 125-130 15-20 3 D0. 770. 125-130 15-20 4 D0. 780. 125-130 15-20 4 Soluble. 790. 125-130 15-20 4 Do. 125-130 15-20 5 D0. 130-135 20-30 Insoluble 130-135 20-30 D0. 130-135 20-30 1% Do. 130-135 20-30 3 D0. 130-135 20-30 2% D0. d 130-135 20-30 2% Do. (1 130-135 20-30 3 Do. d 130-135 20-30 3% Soluble. 1 9d 130-135 20-30 Insoluble.

Table VI'Continued Solubility Time,

hrs.

Kerosene Insoluble.

Do. Dispersible. Insoluble.

Do. Dispersible. Insoluble.

PART 6 The resin condensates which are employed as intermediate reactants are strongly basic. Initial oxyalkylation of these products with a monoepoxide or diepoxide can be accomplished generally, at least in the initial stage, without the addition of the usual alkaline catalyst such as those described in connection with oxyalkylation employing monoepoxides in Part 5 immediately preceding. As a matter of fact, the procedure is substantially the same as using a non-volatile monoepoxide such as glycide or methylglycide. However, during progressive oxyalkylation with a monoepoxide it is usually necessary to use a catalyst as previously described and, thus, there may or may not be suificient catalyst present for the reaction with the diepoxide. Reference to the catalyst present includes the residual catalyst remaining from the oxyalkylation step in which the monoepoxide was'used.

Briefly stated then, employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials, such as caustic soda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind illustrated by iron and tin chloride. Furthermore, insoluble catalysts such as clay or specially prepared mineral catalysts have been used. If for any reason the reaction does not proceed rapidly enough with the diglycidyl ether or other analogous reactant then a small amount of finely divided caustic soda or sodium methylate can be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes without saying that the reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethyleneglycol or the diethylether of propyleneglycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solventfree and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, then xylene or an aromatic petroleum solvent will serve. it the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not oxyalkylation-susceptible. It is easy enough to select a suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the mosteconomical one.

til

Example 12 The product was obtained by reaction between the diepoxide previously described as diepoxide A and oxyalkylated resin condensate 2c. Oxyalkylated condensate 2c has been described in previous Part 5 and was obtained by the oxyetbylation of condensate lb. The preparation of condensate 1b was described in Part 4, preceding. Details have been included in regard to both steps. Conden'sate lb, in turn, was obtained from amine A and resin 2a; amine A was symmetrical dimethyl ethylene diamine and resin 2a, in turn, was obtained from paratertiarybutylphenol and formaldehyde.

in any event, 325 grams of the oxyalkylated resin condensate previously identified as 20 were dissolved in approximately an equal weight of xylene. About 3 grams of sodium methylate were added as a catalyst so the total amount of catalyst present, including residual catalyst from the prior oxyalkylation, was about 3.4 grams. 18.5 grams of diepoxide A were mixed with an equal weight of xylene. The initial addition of the diepoxide solution was made after raising the temperature of the reaction mass to about 108 C. The diepoxide was added slowly over a period of slightly less than one hour. During this time the temperature was allowed to rise to about 127 C. The mixture was allowed to reflux at about 138 C. using a phase-separating trap. A small amount of xylene was removed by means of a phase-separating trap so the refluxing temperature rose gradually to about 160 C. The mixture was refluxed at this temperature for about 5 hours. At the end of this period the xylene which had been removed by means of the phase-separating trap was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on a hot plate in order to examine the physical properties. The material was an amber, or light reddish amber, viscous liquid. It was insoluble in water; it was insoluble in gluconic acid, but it was soluble in xylene and particularly in a mixture of xylene and 20% methanol. However, if the material was dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in a xylene-methanol mixed solvent as previously described, with or without the further addition of a little acetone.

Generally speaking, the solubility of these derivatives is in line with expectations by merely examining the solubility of the preceding intermediates, to wit, the oxyalkylated resin condensates prior to treatment with the diepoxide. These materials, of course, vary from ex tremely water-soluble products due to substantial oxyethylation, to those which conversely are water-insoluble 29 but xylene-soluble or even kerosene-soluble due to high stage oxypropylation. Reactions with diepoxides or poly epoxides of the kind herein described reduce the hydrophile properties and increase the hydrophobe properties, i. e., generally make the products more soluble in kerosene or a mixture of kerosene and xylene, or in xylene, but less soluble in water. Since this is a general rule which applies throughout, for sake of brevity future reference to solubility will be omitted.

The procedure employed, of course, is simple in light of What has been said previously and in effect is a prcedure similar to that employed in the use of glycide or methylglycide as 'oxyalkylating agents. See, for example, Part 1 of U. 8. Patent No. 2,602,062 dated July 1, 1952, to DeGroote.

'Various examples obtained in substantially the same manner are enumerated in the following tables:

Table X Oxyalkyl. Prob. mol. Ex. No. resm conweight of Amount of Amount of densate reaction product, grs. solvent product Table VII Ex. Oxy. Amt., Diep- Amt., Catalyst Xy- Molar Time of Max. No. resin congrs. oxide grs. (NaOCH lene, ratio reaction, temp., Color and physical state densate used grs. V grs. hrs. O.

325 A 18. 6 3. 4 344 2:1 5 160 Reddish amber resinous mass. 271 A 9.3 2.8 280 2:1 5 165 D0. 238 A 18. 5 2. 6 257 2:1 5 168 Do. 301 A 9. 3 3. 1 310 2: 1 5 170 Do. 437 A 9. 3 4. 5 446 2: 1 1 5 162 Do. 325 A 18. 5 3. 4 344 2:1 5. 5 165 Do. 379 A 9. 3 3. 9 388 2: 1 5. 5 160 Do. 238 A 18. 5 2. 6 257 2: 1 5 168 D0. 421 A 9. 3 4. 3 430 2:1 5 168 Do. 364 A 9. 3 3. 7 373 2:1 4. 5 170 Do. 379 A 18. 5 4. 0 398 2: 1 4.5 170 Do. 243 A 9. 3 2. 5 252 2:1 4. 5' 170 Do. 428 A 9. 3 4. 4 437 2:1 4. 5 172 D0. 406 A 9.3 4.2 415 2:1 5 160 Do. 180 A 1. 9 1. 8 182 2:1 4 170 Do.

Table VIII Ex. Oxy. Amt, Diep- Amt, Catalyst Xy- Molar Time of Max.

0. resin congrs. oxide g'rs. (NaOOH lene, ratio reaction, temp., Color and. physical state densate used grs. grs. hrs. O.

325 B 11 3. 4 336 2:1 5 165 Reddish amber resinous mass. 271 B 5.5 2.8 277 2:1 4 170 Do. 238 B 11 2.5 249 2:1 4 172 Do. 301 B 5. 5 3. 1 1 307 2:1 4 175 Do. 437 B 5. 5 4. 4 443 2: 1 5 168 Do. 325 B 11 3.4 336 2:1 4 170 Do. 379 B 5. 5 3. 9 385 2: 1 4 170 Do. 238 B 11 2. 5 249 2:1 i 4 175 Do. 421 B 5. 5 4. 3 427 2: 1 4 170 Do. 364 B 5. 5 3. 7 370 2: 1 4 172 Do. 379 B 11 3. 9 390 2:1 4 174 Do. 243 B 5.5 2. 5 249 2:1 5 170 D0. 428 B 5.5 4.3 434 2:1 5 172 Do. 406 B 5. 5 4.1 412 2: 1 5 170 D0. 180 B 1.1 1. 8 181 2: 1 5 168 Do.

' Table IX At times we have found a tendency for an insoluble 1k 1 P b 1 mass to form or at least to obtain inciplent cross-linking Oxya y. rc.mo. resin com Weight of Amount of Amount of or gelhng even when the molal ratio 1s m the order of 2 densate reaction product, grs. solvent moles of resin to one of dlepoxide. We have found this Product can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or i both, with an inert solvent, such as xylene or the like.

51120 2,550 1,280 In some mstances an oxygenated solvent, such as the Egg 3 fig diethylether of ethyleneglycol may be employed. An-

7 1 Y I a a 6, 60 3,430 1, 715 other procedure wh1ch is helpful 1s to reduce the amount g igg g: of catalyst used, or reduce the temperature of reaction 17,230 3, 446 1,723 7 by adding a small amount of initially lower boiling sol- @1328 3; h3g2 vent, such as benzene, or use benzene entirely. Also, we 9,838 233 2,411; have found it desirable at times to use slightly less than 161600 3:320 1:660 apparently the theoretical amount of dlepoxlde, for in- 36,370 3,637 819 stance, to mstead of The reason for this fact may reside in thepossibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule actually .may vary from the true molecular weight by several percent.

The condensate can be depicted in a simplified form which, for convenience, may be shown thus:

(Amine)CH (Resin)CH (Amine) If such product is subjected to oxyalkylation reaction it involves the phenolic hydroxyls of the resin structure and, thus, can be depicted in the following manner:

(Amine) CH Oxyalkylated Resin) CH (Amine) Following such simplification the reaction with a polyepoxide, and particularly a diepoxide, would be depicted thus:

(Amine) OHa(OxyalkylaIted Resin) CH2 (Amine) [(Amine) CH (Resin)] This product, since it is susceptible to oxyalkylation by means of the oxyalkylated phenolic hydroxyl groups and depending on the selection of the amine, may be .susceptible to oxyalkylation in event a hydroxylated amine or polyamine had been used, and may be indicated in the following manner:

[oxyalkylated (Amine) CH Resin) F' "I Oxyalkylated(Amine)CHAResin) Likewise, it is obvious thatthe two different types'of oxyalkyla-tion-susceptible compounds may combine so to give molecules which may be indicated thus:

EminQOHflOxyalkylated Resin) CHKAmine) i l l Oxyalkylated (Amine) CH2 Resin) 0 xyalkylated (Amine) CHz(Amine) L l (Amine) (lHflOxyalkylated Resin) OHz(Amine) O xyalkylated (Amine)'0 Hz (Amine) l l Oxyalkylated(Amine)'CH2(Resin) Oxyalkylated (Amine) CHKAmine) L l oxyalkylated (Amine) CHflAmine) Actually, the product obtained by reaction with a diglycidyl ether could show considerably greater complexity due to the fact that, as previously pointed out, the condensate reaction probably does not yield a hundred percent condensate in absence of other byproducts. All this simply emphasizes one fact, to wit, that there is no suitable method of characterizing the final reaction product except in terms of method of manufacture.

PART 7 As to the use of conventional demulsifying agents reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and effect to the instant process, noting only that where reference is made to Example 13b in said text beginning incolumn l5 andending in column 18, reference should be to Example 4e,herein described.

PART 8 The products, compounds, or the like, herein described can be employed for various purposes and particularly for the resolution of petroleum emulsions of the water-in-oil type as described in detail in 'Part Seven, preceeding.

Such products can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an imine one may employ what is a somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure wherein R and R" are alkyl groups.

-It is not necessary to point out that, after reaction with a reactant of the kind described which introduces a basic nitrogen atom, the resultant product can be employed for the resolution of emulsions of the water-in-oil type as described in Part Seven preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by reaction with a polyepoxide and certain specified oxyalkylated products obtained in the manner described inPart .Six, preceding, it is to be noted that .in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for .oils, .fats, and waxes, as ingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, drying, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. .These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial resin, the particular monoepoxide selected and the ratio of monoepoxide to resin, together with the particular polyepoxide employed, result in a variety of materials which are useful as wetting agents or surface tension reducing agents; as detergents, emulsifiers or dispersing agents; as additives for lubricants, both of the natural petroleum type and the synthetic type, as additives in the flotation of ores, and at times as aids in chemical reactions insofar that demulsification is produced between the insoluble reactants. Furthermore, such products can be used for a variety of other purposes, including use as corrosion inhibitors, defoamers, asphalt additives, and at times even in the resolution of oil-inwater emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insoluble phases.

The products herein described can be reacted with polycarboxy acids, such as phthalic acid or anhydride, maleic acid or anhydride, diglycolic acid, and various tricarboxy and tetracarboxy acids so as to yield acylated derivatives, particularly if one employs one mole of the polycarboxy acid for each reactive hydroxyl radical present in the final polyepoxide-treated product. Thus, one obtains a comparatively large molecule in which there is a plurality of carboxyl radicals. Such acidic fractional esters are suitable for the resolution of petroleum emulsions of the water-in-oil type as herein described.

Having thus described our invention what wev claim as new and desire to secure by Letters Patent is:

l. A three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide; said first manufacturing step being a method of (A) condensing (a) a fusible, nonoxygenated organic solvent-soluble, waterinsoluble, phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having up to 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical, and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable; followed as a second step by (B) oxyalkylation by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and then completing the reaction by a third step of (C) reacting said oxyalkylated resin condensate with nonaryl hydrophile polyepoxides containing at least two 1,2-epoxy rings and having two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a water-soluble polyhydric alcohol by the radical said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; with the further proviso that said reactive monoepoxidederived compounds (AA) and nonaryl polyepoxides (BB) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; said reaction between (AA) and (BB) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl polyepoxide.

2. The product obtained by the method described in claim 1.

3. A three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide; said first manufacturing step being a method of (A) condensing (a) a fusible, nonoxygenated organic solvent-soluble, Waterinsoluble, phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial "absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having up to 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heatstable; followed as a second step by (B) oxyalkylation by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and then completing the .reaction by a third step of (C) reacting said oxyalkylated resin condensate with nonaryl Ihydrophile polyepoxides containing at least two 1,2-epoxy rings and having two terminal 1,2-cpoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a water-soluble polyhydric alcohol by the radical said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane ringsis free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said polyepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive monoepoxide-derived comr, 35 pounds (AA) and nonaryl polyepoxides (BB) be members of the class consisting of non-thermosetting organic solvent-solubleliquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and "solids melting below the point of pyrolysis; said reaction between (AA) and (BB) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl polyepoxide.

4. A three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a diepoxide; said first manufacturing step being a method of (A) condensing (a) a fusible. nonorganic solvent-soluble, water-insoluble, phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having up to 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine' be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical, and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso thatthe resinous condensation product resulting from the process be heatstable; followed as a second step by (B) oxyalkylation by means of an alpha-beta alkylene'oxide having not more than 4 carbon atoms and selected from the class consisting of ethyleneoxide, propylene oxide, butylene oxide, glycide and methylglycide; and then completing the L reaction by a third step of (C) reacting said oxyalkylated resin condensate with nonaryl hydrophile diepoxides containing two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a watersoluble polyhydric alcohol by the radical H H H -o ---on said diepoxide being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single'chain. said diepoxides being characterized by having present not more than carbon atoms; with the further proviso that said reactive monoepoxide-derived compounds (AA) and nonaryl diepoxides (BB) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; said reaction between (AA) and (BB) be conducted below the pyrolytic 36 point of the reactants andthe resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the o-Xyalkylated resin condensate to 1 mole of the nonaryl diepoxide.

5. The process of claim 4 wherein the diepoxide contains at least one reactive hydroxyl radical.

6. A three-step manufacturing process involving (1) condensation; 2) oxyalkylation with a monoepoxide; and (3) oxyaliiylation with a diepoxide; said first manufacturing step being a method of (A) condensing (a) a fusible, nonoxygenated organic solvent-soluble, water-insoluble, phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional oniy in regard to methylol-forrning reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trir'unctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (11) a basic nonhydroxylated polyamine having at least one secondary amino group and having up to 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted irnidazoline radical, and any substituted tetrahydro-pyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyroiytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation pro-duct resulting from the process be heatstable; followed as a second step by (B) oxyalkylation by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and then completing the reaction by a third step of (C) reacting said oxyalkylated resin condensate with a hydroxylated diepoizypolyglycerol containing two terminal 1,2-epoxy rings and having not more than 20 carbon atoms; with the forth: proviso that said monc-epoxide-derived compounds (AA) and said hydroxylated diepoxyglycerol (BB) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction prod not be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; said reaction between (AA) and (BB) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylatcd resin condensate to 1 mole of the hydroxylated diepoxyglycerol.

7. The method of claim 6 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group. and the precursory aldehyde is formaldehyde, and the total number of phenolic nuclei in the initial resin are not over 5.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A THREE-STEP MANUFACTURING PROCESS INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A MONOEPOXIDE; AND (3) OXYALKYLATION WITH A POLYEPOXIDE; SAID FIRST MANUFACTURING STEP BEING A METHOD OF (A) CONDENSING (A) A FUSIBLE, NONOXYGENATED ORGANIC SOLVENT-SOLUBLE, WATERINSOLUBLE, PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 